ChemCatChem,
Journal Year:
2024,
Volume and Issue:
unknown
Published: Nov. 5, 2024
Abstract
Herein,
we
have
reported
a
sustainable
and
chemo‐selective
strategy
for
the
synthesis
of
functionalized
branched
alcohols.
A
commercially
available
catalytic
system
does
not
need
any
special
ligand
liberated
water
hydrogen
as
side
products.
series
alkyl
primary
alcohols
(C4–C10),
including
methanol,
were
tolerated
in
good
to
high
yield.
Sequential
transformations
substituted
pyrroles,
chromenes
donepezil
drug
obtained
(>57
entries).
Preliminary
mechanistic
investigations
performed
understand
pathways.
Angewandte Chemie International Edition,
Journal Year:
2023,
Volume and Issue:
62(26)
Published: April 21, 2023
A
homogeneous
manganese-catalyzed
cross-coupling
of
two
secondary
alcohols
for
the
divergent
synthesis
γ-disubstituted
and
β-disubstituted
ketones
is
reported.
Employing
well-defined
Mn-MACHOPh
as
catalyst,
this
novel
protocol
has
a
broad
substrate
scope
with
good
functional
group
tolerance
affords
diverse
library
valuable
disubstituted
in
moderate
to
yields.
The
strong
influence
reaction
temperature
on
selective
formation
alcohol
products
was
theorized
preliminary
DFT
studies.
Studies
have
shown
that
Gibbs
free
energy
thermodynamically
more
favourable
than
corresponding
at
lower
temperature.
Angewandte Chemie International Edition,
Journal Year:
2024,
Volume and Issue:
63(13)
Published: Feb. 1, 2024
Abstract
The
synthesis
of
mono‐
N
‐methylated
aliphatic
primary
amines
has
traditionally
been
challenging,
requiring
noble
metal
catalysts
and
high‐pressure
H
2
for
achieving
satisfactory
yields
selectivity.
Herein,
we
developed
an
approach
the
selective
coupling
methanol
amines,
without
hydrogen,
using
a
manganese‐based
catalyst.
Remarkably,
up
to
98
%
with
broad
substrate
scope
were
achieved
at
low
catalyst
loadings.
Notably,
due
weak
base‐catalyzed
alcoholysis
formamide
intermediates,
our
novel
protocol
not
only
obviates
addition
but
also
prevents
side
secondary
‐methylation,
supported
by
control
experiments
density
functional
theory
calculations.
ACS Catalysis,
Journal Year:
2024,
Volume and Issue:
14(6), P. 4018 - 4029
Published: Feb. 28, 2024
Chemoselective
synthesis
of
functionalized
gem-β,β′-bis(alkyl)alcohols
by
coupling
a
β-alkylated
secondary
alcohol
with
primary
is
reported
using
nickel
via
sequential
DCR
(dehydrogenation–condensation–rehydrogenation)
approach.
Using
our
method,
1-arylethanol
and
benzyl
alcohols
undergo
one-pot
successive
double
alkylation
reaction
to
form
alcohols.
Methanol,
C2–C12
alcohols,
citronellol,
fatty
acid-derived
oleic
are
tolerated,
including
late-stage
functionalization
steroid
hormones
(cholesterol
testosterone)
5-pregnen-3β-ol-20-one.
The
catalytic
transformations
enabled
the
donepezil
drug
(used
for
Alzheimer's
disease),
N-heteroarenes
(quinoline
acridine),
chromane
intermediate
flavan
derivatives.
Hammett
kinetic
plot
analysis
differently
p-substituted
1-phenyl
propanol
indicated
that
oxidation
might
be
rate-determining
step
expected
strong
influence
substitution
on
kinetics.
A
negative
ρ
value
(−0.60)
strongly
signify
formation
positive
charge
alcohol.
Preliminary
mechanistic
investigation
revealed
dehydrogenation
aldehyde
as
it
involves
C–H/D
bond
breaking
alcohol,
PH/PD
6.0
was
calculated.
Reaction
profile
studies,
EPR
experiments,
Hammett-plot
cyclic
voltammetry,
UV–visible
XPS
analysis,
structural
electronic
changes
at
Ni-center
well
behavior
catalysts
during
progress
reactions.
Journal of the American Chemical Society,
Journal Year:
2023,
Volume and Issue:
145(47), P. 25545 - 25552
Published: Nov. 14, 2023
Herein,
we
report
a
manganese-catalyzed
three-component
coupling
of
β-H
containing
alcohols,
methanol,
and
phosphines
for
the
synthesis
γ-hydroxy
via
borrowing
hydrogen
strategy.
In
this
development,
methanol
serves
as
sustainable
C1
source.
A
variety
aromatic
aliphatic
substituted
alcohols
could
undergo
dehydrogenative
cross-coupling
process
efficiently
deliver
corresponding
β-phosphinomethylated
alcohol
products
in
moderate
to
good
yields.
Mechanistic
studies
suggest
that
transformation
proceeds
sequential
manner
including
catalytic
dehydrogenation,
aldol
condensation,
Michael
addition,
hydrogenation.
Organic & Biomolecular Chemistry,
Journal Year:
2024,
Volume and Issue:
22(19), P. 3860 - 3865
Published: Jan. 1, 2024
The
aminophosphinoylation
of
alcohols
with
amines
and
H-phosphine
oxides
provides
an
efficient
mild
approach
to
access
various
α-aminoalkylphosphine
in
good
yields
tolerance
functional
groups
using
H
2
O
as
a
clean
solvent.
Nature Communications,
Journal Year:
2024,
Volume and Issue:
15(1)
Published: Aug. 9, 2024
Cyclopropanes
are
among
the
most
important
structural
units
in
natural
products,
pharmaceuticals,
and
agrochemicals.
Herein,
we
report
a
manganese-catalyzed
cyclopropanation
of
allylic
alcohols
with
sulfones
as
carbene
alternative
precursors
via
borrowing
hydrogen
strategy
under
mild
conditions.
Various
arylmethyl
trifluoromethyl
work
efficiently
this
transformation
thereby
deliver
corresponding
cyclopropylmethanol
products
58%
to
99%
yields.
Importantly,
major
benefit
is
that
versatile
free
alcohol
moiety
retained
resultant
which
can
undergo
wide
range
downstream
transformations
provide
access
series
functional
molecules.
Mechanistic
studies
support
sequential
reaction
mechanism
involves
catalytic
dehydrogenation,
Michael
addition,
cyclization,
hydrogenation.
Organic Chemistry Frontiers,
Journal Year:
2024,
Volume and Issue:
11(9), P. 2613 - 2623
Published: Jan. 1, 2024
A
Ru-catalyzed
selective
hydroacylation
of
acrylonitriles
with
aldehydes
or
alcohols
towards
β-ketonitriles
is
established.
Glutaronitriles
can
be
obtained
through
a
one-step
tandem
and
Michael
addition
acrylonitrile
alcohols.
Organic Letters,
Journal Year:
2024,
Volume and Issue:
unknown
Published: Dec. 10, 2024
Herein,
a
photocatalytic
strategy
for
the
synthesis
of
secondary
alcohols
by
nucleophilic
addition
an
alkene
with
aldehyde
is
described.
This
operationally
simple
methodology
opens
approach
using
commercially
available
reagents
in
moderate
to
excellent
yields.
Mechanistic
studies
indicate
that
formation
radical
anion
from
via
single-electron
transfer
key
step
this
reaction.
